Role of Fe(III), phosphate, dissolved organic matter, and nitrate during the photodegradation of domoic acid in the marine environment

The photodegradation of domoic acid in model seawater containing varying amounts of total Fe(lll) (expressed as Fe(lll)), NO(3-), total phosphate (expressed as P04(3-)), and dissolved organic matter (DOM) is reported. A multivariate, microscale, high-throughput experimental approach is described for evaluating how these components interact to control the removal of domoic acid from natural waters. Under the nominal conditions of the study ([Fe(lll)]o 0-4 microM; [N03-]o 0-35 microM; [P04(3-)]o 0-4 microM; [DOM]o 0-10 mg/ L), it is apparent that Fe(lll) and DOM are significant promoters of domoic acid photooxidation. In contrast, P04(3-) interacts with Fe(lll) to inhibit the photooxidation of domoic acid, but P04(3-) alone does not act to slow or accelerate domoic acid photodegradation. No other variables (singly or interactively) have a statistically significant impact. At an incident light intensity of 765 W/m2 and initial domoic acid concentration of 0.96 microM, domoic acid half-lives range over 12-36 h, with half-life a function of [Fe(III)], [PO4(3-)], and dissolved organic matter loadings. An NMR based technique for measuring domoic acid-Fe(lll) binding (1.72 x 10(11)) is reported.     

Photochemical oscillation of Fe(II)/Fe(III) ratio induced by periodic flux of dissolved organic matter

Variation of iron species in the UV-irradiated aqueous solution was examined in the presence of various dissolved organic matter (DOM). Under the irradiation at constant light intensity, a regular oscillation in the ratio of Fe(II) to total iron, Fe(II)/Fe(t), was observed when DOM was periodically added into the solution. In each cycle, the Fe(II)/Fe(t) ratio increased initially and then decreased with concomitant degradation of DOM. The Fe(II)/Fe(t) ratio approached a constant value after the DOM was completely mineralized. The period and amplitude of the oscillation were dependent on DOM structure and its initial concentration, but the ultimate photosteady state was not affected by DOM. It was revealed that both DOM and photoreactive Fe(III) species were indispensable for the fluctuation in Fe(II)/Fe(t) ratio. The ultimate photosteady state originated from the equilibrium between Fe(III) photoreduction and aerobic Fe(II) photooxidation induced simultaneously by UV irradiation. It was the DOM that disturbed these two opposite processes, leading to the oscillation in Fe(II)/ Fe(t) ratio under UV irradiation.     

Role of dissolved organic matter, nitrate, and bicarbonate in the photolysis of aqueous fipronil

A multivariate kinetic model of aqueous fipronil photodegradation was developed as a function of dissolved organic matter (DOM), bicarbonate, and nitrate at concentrations that bracketthose commonly observed in natural waters (ca. 0-10 mg/L). Several pathways were available for fipronil photodegradation in this system, including direct photolysis and indirect photooxidation by species produced during the illumination of natural waters (e.g., 3NOM*, 1O2*, *OH, *CO3(1-), *OOR, *OOH, e(aq)-, O2(*-)). Product studies indicated thatfipronil was quantitatively converted to fipronil desulfinyl, a product that is associated with direct photolysis alone. DOM was the only variable that affected fipronil degradation; it decreased the rate of fipronil photodegradation primarily through competitive light absorption (i.e., attenuation) and the quenching of fipronil*. The addition of sodium chloride (30 percent per thousand) resulted in a more rapid rate (approximately 20%) of fipronil loss in comparison to equivalent experiments performed without sodium chloride, implying that fipronil may be more photolabile in marine environments.     

Indirect photodegradation of dissolved free amino acids: the contribution of singlet oxygen and the differential reactivity of DOM from various sources

The role of photochemically generated singlet oxygen (1O2) in the DOM-sensitized degradation of eighteen dissolved free amino acids was investigated. The fraction of total sensitized degradation due to reaction with 1O2 was determined through a kinetic analysis based on a measured reaction rate constant for each amino acid coupled with measured 1O2 concentrations and was confirmed through quenching experiments. Only four of the eighteen free amino acid residues examined were found to be photolabile under environmentally relevant conditions: histidine, methionine, tyrosine, and tryptophan. The fraction of Suwannee River Humic Acid (SRHA)-sensitized degradation due to reaction with 1O2 ranged from an upper value of 110 +/- 10% for histidine to 8 +/- 1% for tryptophan, with 26 +/- 3% contribution for methionine and 33 +/- 4% for tyrosine. In addition to degradation through reaction with 1O2, other reactive intermediates involved in the SRHA-photosensitized degradation of these amino acids were identified. Methionine was thought to be additionally degraded through reaction with H2O2 and triplet excited-state DOM, and 67% of tyrosine's indirect photodegradation was assigned to an oxygen-dependent type I photooxidation reaction. The majority of tryptophan indirect degradation was due to reaction with 3DOM. Photodegradation experiments with various DOM sources including Pony Lake (Antarctica) fulvic acid and a synthetic estuarine sample, as well as Minnesota freshwater samples (lakes Itasca, Superior, Josephine, and the St Louis River), demonstrated distinct reactivity patterns, indicating that DOM's 1O2-generation efficiency is not strongly coupled to its ability to promote other photooxidation pathways. These four amino acids highlightthe differential photoreactivity of DOM from various sources.     

Hydroxyl radical production via the photo-Fenton reaction in the presence of fulvic acid

The photo-Fenton reaction, the reaction of photoproduced Fe(II) with H2O2 to form the highly reactive hydroxyl radical (OH*), could be an important source of OH* in sunlit natural waters. To determine if the photo-Fenton reaction is significant in mildly acidic surface waters, we conducted experiments simulating conditions representative of natural freshwaters using solutions of standard fulvic acid and amorphous iron oxide at pH 6.0. A probe method measuring 14CO2 produced by the reaction of 14C-labeled formate with OH* was used to detect small OH* production rates without otherwise influencing the chemical reactions occurring in the experiments. Net H2O2 accumulation was simultaneously measured using an acridinium ester chemiluminescence method. Measured losses of H2O2 by reaction with Fe(II) in dark experiments produced approximately the expected quantities of OH*. The difference between H2O2 accumulation in the presence and absence of Fe(III) in fulvic acid solutions exposed to light was interpreted as the loss of H2O2 by reaction with photoproduced Fe(II), consistent with measured OH* production rates. The Fe ligand desferrioxamine mesylate eliminated both OH* production and H2O2 photoloss induced by Fe. Our results imply that when Fe is a major sink of H2O2, the photo-Fenton reaction is likely to be the most important source of OH*, leading to a significant sink of organic compounds in a wide variety of sunlit freshwaters.     

Efficient decomposition of perfluorocarboxylic acids and alternative fluorochemical surfactants in hot water

Decomposition of C5-C9 perfluorocarboxylic acids (PFCAs) and perfluoroether carboxylic acids (alternatives to PFCA-based surfactants) in hot water in a sealed reactor was investigated. Although PFCAs showed almost no decomposition in hot water at 80 degrees C in the absence of persulfate (S2O8(2-)), the addition of S2O8(2-) to the reaction system led to efficient decomposition, even at this relatively low temperature. The major products in the aqueous and gas phases were F- ions and CO2, respectively, and short-chain PFCAs were also detected in the aqueous phase. For example, when an aqueous solution containing perfluorooctanoic acid (PFOA, 374 microM) and S2O8(2-) (50.0 mM) was heated at 80 degrees C for 6 h, PFOA concentration in the aqueous phase fell below 1.52 microM (detection limit of HPLC with conductometric detection), and the yields of F- ions [i.e., (moles of F- formed) /(moles of fluorine content in initial PFOA)] and CO2 [i.e, (moles of CO2 formed) /(moles of carbon content in initial PFOA)] were 77.5% and 70.2%, respectively. This method was also effective in decomposing perfluoroether carboxylic acids, such as CF3OC2F4OCF2COOH, CF3OC2F4OC2F4OCF2COOH, and C2F5OC2F4OCF2COOH, which are alternatives to PFCA-based surfactants, producing F- and CO2 with yields of 82.9-88.9% and 87.7-100%, respectively, after reactions at 80 degrees C for 6 h. In addition, the method was successfully used to decompose perfluorononanoic acid in a floor wax solution. When PFOAwastreated at a higher temperature (150 degrees C), other decomposition reactions occurred: the formation of F- and CO2 was dramatically decreased, and 1H-perfluoroalkanes (C(n)F(2n+1)H, n = 4-7) formed in large amounts. This result clearly indicates that treatment with high-temperature water was not suitable for the decomposition of PFCAs to F-: surprisingly, the relatively low temperature of 80 degrees C was preferable.     

Complete oxidation of benzene in gas phase by platinized titania photocatalysts

Photocatalytic oxidation of benzene in gas phase was carried out with a flow reactor at room temperature. In a humidified airstream ([H2O] = 2.2%), benzene was quantitatively decomposed to CO2 over UV-irradiated 1.0 wt %-Pt/TiO2 catalyst. When the benzene conversion was decreased, the selectivity to CO2 was decreased, while that to CO was increased. As the amount of Pt loaded on the TiO2 catalyst was increased, the rate of the CO photooxidation was increased, while that of benzene photooxidation was almost unchanged. These findings showed that the photooxidation of benzene to CO2 over Pt/TiO2 catalyst proceeded by the two sequential steps: (i) benzene was decomposed to CO2 and CO with the selectivities of 94% and 6%, respectively, and (ii) CO was subsequently oxidized to CO2. The rate of CO photooxidation over Pt/TiO2 catalyst was greatly decreased by the presence of benzene in the reaction gas stream. The complete oxidation of benzene to CO2 could be also achieved by using the hybrid catalysts comprising pure TiO2 and platinized TiO2.     

Heterogeneous photochemistry of oxalic Acid on mauritanian sand and icelandic volcanic ash

Teragram quantities of crustal and volcanic aerosol are released into the atmosphere on an annual basis. Although these substrates contain photoactive metal oxides, little is known about the role that they may play in catalyzing the heterogeneous phototransformation of semivolatile organic species. In the present study, we have investigated oxalic acid photochemistry at the surface of Fe(2)O(3), TiO(2), Mauritanian sand, and Icelandic volcanic ash in the presence and absence of oxygen using a photochemical Knudsen cell reactor. Illumination of all sample types resulted in the production of gas-phase CO(2). In the case of Mauritanian sand, the production of gas-phase CO(2) scaled with the loss of surface oxalic acid. In the absence of oxygen, the production of CO(2) by the sand and ash films scaled with the absorption spectrum of iron oxalate, which suggests that the reaction is at least in part iron-mediated. The presence of oxygen suppressed CO(2) production at the Fe(2)O(3) surface, enhanced CO(2) production at the Mauritanian sand surface, and did not have a net effect upon CO(2) production at the Icelandic ash surface. These different oxygen dependencies imply that oxalic acid photochemistry at the authentic surfaces under study was not solely iron-mediated. Experiments at the TiO(2) surface, which showed enhanced CO(2) production from oxalic acid in the presence of oxygen, suggest that Ti-mediated photochemistry played an important role. In summary, these results provide evidence that solid-phase aerosol photochemistry may influence the atmospheric lifetime of oxalic acid in arid regions, where its removal via wet deposition is insignificant.     

Effect of carbon dioxide on autoxidation and photooxidation of nitrosylmyoglobin

Autoxidation and photooxidation of nitrosylmyoglobin, MbFe(II)NO, the pigment of nitrite-cured meat, was investigated in aqueous solution saturated with gas mixtures containing varying levels of CO(2) (0%, 20% and 90%) in the presence of either 1.5 or 10% O(2) and balanced with N(2) in order to mimic modified atmosphere (MA) packaging of meat products. Quantum yields for photooxidation at 1.5% O(2) for monochromatic UV-light (366 nm) were slightly higher than for visible light (436 nm) in agreement with previous findings, while the quantum yields showed no dependence on the CO(2) levels. Autoxidation of MbFe(II)NO was evaluated by global analysis of spectral data applying a kinetic model with two consecutive reaction steps, and the second rate constant was significantly reduced at the highest CO(2) level investigated, while the rate constant of the initial reaction step was found independent of the CO(2) levels. The varying dependence observed for autoxidation and photooxidation of MbFe(II)NO in relation to CO(2) level confirms the differing reaction mechanisms for the two types of MbFe(II)NO degradation. Photooxidation of nitrite-cured meat products packed in MA is accordingly expected to be independent of the presence of varying CO(2) levels, while thermal oxidation (autoxidation) of MbFe(II)NO is reduced at elevated levels of CO(2), which may be of some relevance during product storage and retail display.     

高CO_2结合低O_2贮藏对杏鲍菇谷氨酸代谢的影响

谷氨酸属于杏鲍菇中的鲜味氨基酸,为探讨高CO_2结合低O_2贮藏对杏鲍菇谷氨酸代谢的影响,以空气气体比例为对照(CK),用不同的气体组分[CA1(2%O_2)、CA2(2%O_2+10%CO_2)、CA3(2%O_2+30%CO_2)、CA4(2%O_2+50%CO2)]对杏鲍菇进行气调处理,研究了贮藏期间菇体丙二醛含量及抗氧化酶活性的变化,结合聚类分析表明CA3(2%O_2+30%CO_2)处理对减缓采后杏鲍菇的衰老具有重要的作用。进一步分析了CA3处理对杏鲍菇表型、呼吸速率、游离氨基酸含量、味觉变化及蛋白酶、谷氨酸合酶(GOGAT)、脯氨酸脱氢酶(PRODH)和谷氨酸脱氢酶(GDH)活性的影响。结果表明,较对照相比,CA3处理降低了采后杏鲍菇的呼吸速率,增加了其总游离氨基酸及谷氨酸含量,从而维持了菇体的滋味品质;另外,该CA3处理抑制了采后杏鲍菇蛋白酶、GOGAT、PRODH和GDH的活性。可见,2%O_2+30%CO_2贮藏可维持采后杏鲍菇的鲜味特征,该作用与其抑制GDH的活性有关。     

刺参多糖清除活性氧保护线粒体的研究

本文采用酶解法(胃蛋白酶与胰蛋白酶)提取刺参多糖(Stichopus japonicus polysaccharides,SJP),以硫酸苯酚法测定多糖含量并研究其清除活性氧保护线粒体的作用机制。以Fe~(2+)-Vit C系统诱发肝线粒体脂质过氧化,以丙二醛(MDA)为指标测定SJP对脂质过氧化的影响;测定SJP的还原力及其对Fe~(2+)的螯合作用;以H_2O_2-Fe~(2+)体系为羟自由基(·OH)生成系统,测定SJP清除·OH的能力;用滴定法测定SJP清除过氧化氢(H_2O_2)的能力;用氮蓝四唑(NBT)法测定SJP清除超氧阴离子(O_2·~-)的能力。研究表明:SJP可抑制MDA生成;SJP具有一定的还原力和较弱的Fe~(2+)螯合作用;另外,SJP能在一定浓度范围内明显清除·OH、H_2O_2和O_2·~-。SJP能通过抗氧化、清除活性氧(ROS)来保护线粒体,具有保护机体的功效,这是SJP保护线粒体的可能机制。     

Degradation pathways of pentachlorophenol by photo-Fenton systems in the presence of iron(III), humic acid, and hydrogen peroxide

The degradation characteristics and pathways of pentachlorophenol (PCP) by the photo-Fenton systems were studied in H2O2 aqueous solutions, which contained Fe(III) only [H2O2/Fe(III) system] and Fe(III) + humic acid (HA) [H2O2/Fe(III)/HA system] at pH 5.0. Although 40% of the PCP was degraded after 5 h of irradiation in the H2O2/Fe(III) system, more than 90% was degraded in the H2O2/Fe(III)/HA system. This shows that at pH 5.0 the degradation of PCP is clearly enhanced by the presence of HA in the photo-Fenton system. In the H2O2/Fe(III) system, the production of octachlorodibenzo-p-dioxin (OCDD) was detected, and 2-hydroxy nonachlorodiphenyl ether was also identified as a precursor of OCDD. However, no OCDD production was observed in the H2O2/Fe(III)/HA system. This indicates that the presence of HA represses the production of OCDD during the degradation of PCP by the photo-Fenton system. Such an effect by HA can be attributed to a reaction sequence wherein reaction intermediates derived from PCP, such as PCP., are incorporated into HA. This was verified by 13C NMR and pyrolysis-GC/MS studies.     

Application of spinel-type cobalt chromite as a novel catalyst for combustion of chlorinated organic pollutants

Various chromium-containing catalysts were tested for the total oxidation of trichloroethylene (TCE) as a model reaction for the catalytic combustion of chlorinated organic pollutants. A spinel-type cobalt chromite (CoCr2O4) among others was proven to be a very promising catalyst showing higher activity and higher CO2 selectivity than traditional alumina supported chromia. Even if both Cr3+ and Cr6+ species were observed on the surface of CoCr2O4, the Cr6+ species was stable under reducing environment. The presence of Cr3+-Cr6+ pair sites and the effect of redox treatments on the activity were investigated to explain the nature of possible active sites for TCE decomposition. Higher selectivity to CO2 of CoCr2O4 was ascribed to the abundance of its Cr3+ species, together with its activity for water gas shift reaction.     

箱式气调贮藏对鲜切富士苹果抗氧化系统的影响

以富士苹果为试材,研究了鲜切富士苹果在5℃的5%O2+5%CO2或5%O2+10%CO2箱式气调贮藏条件下抗氧化系统的变化情况。每3d测定1次酶促防御系统的酶活性和非酶促防御系统的抗氧化物质的含量,并测定呼吸速率、腐烂率和褐変情况。结果表明:与对照相比,2种CO2浓度的箱式气调贮藏条件均可启动酶促防御系统,使过氧化物酶(POD)、过氧化氢酶(CAT)和超氧化物歧化酶(SOD)的活性得到提高,同时也加速了非酶促防御系统抗氧化物质的消耗,降低了总酚和Vc含量以及贮藏中后期的还原型谷胱甘肽(GSH)含量。2种浓度的CO2处理可有效减慢呼吸速率,抑制腐烂的发生并有效降低褐变程度,其中5%O2+5%CO2更有利于鲜切富士苹果褐変的控制,而5%O2+10%CO2更有利于抑制腐烂。     

O2/CO2气调下西兰花能量代谢与贮藏品质的关系

能量在果蔬保鲜及衰老过程中起着至关重要的作用,为研究O2/CO2气调对西兰花能量代谢及保鲜效果的影响,本实验以自然空气为对照（CK）,研究体积分数20% O2＋80% CO2、50% O2＋50% CO2、80% O2＋20% CO2气调环境对西兰花10 ℃贮藏过程中pH值和丙酮酸脱氢酶（pyruvate dehydrogenase,PDH）、琥珀酸脱氢酶（succinate dehydrogenase,SDH）和细胞色素c氧化酶（cytochrome c oxidase,CCO）活力及能荷水平、色调（H值）、VC含量和水分质量分数的影响。结果表明：与50% O2＋50% CO2处理组相比,过高比例的CO2（20% O2＋80% CO2）处理可引起西兰花pH值的明显降低,进而造成PDH、SDH和CCO活力的下降和能荷水平的降低,最终造成贮藏期间西兰花VC含量、色调和水分质量分数的下降;过高比例的O2（80% O2＋20% CO2）处理虽在贮藏前期提高了PDH、SDH和CCO活力,但在后期迅速下降,不利于建立平稳而持续的能量供应体系。适宜的O2/CO2气调如50%O2＋50% CO2则可调节西兰花体内pH值和呼吸关键酶活力,建立持续稳定的能量供应体系并很好地维持西兰花贮藏品质。相关性分析表明,能荷水平与西兰花VC含量、色调和水分质量分数具有很高的正相关性,相关系数最高达0.996,因此,能荷变化可作为判断西兰花贮藏条件优劣的衡量指标。     

冰温结合气调包装对牛肉品质的影响

本文以牛肉为研究对象,以冰温技术结合O2/CO2气调包装技术对其进行贮藏保鲜试验,并对贮藏过程中牛肉的菌落总数、挥发性盐基氮(TVB-N)含量、色差值(L*值、a*)以及汁液流失率进行定期测定,同时从色泽和气味方面做以感官评价。结果表明:50%O2+50%CO2组和30%O2+70%CO2组在货架期上要高于对照组和80%O2+20%CO2组至少4 d;但是各组的TVB-N值之间无显著性差异;高浓度的氧气使得汁液流失率增大,不利于牛肉水分的保持;同时,高浓度的O2使牛肉在贮藏早期有很好的颜色,但是贮藏后期在色泽上劣变较快,并加速了牛肉的腐败变质,从而加速了不良气味的产生。高浓度的CO2不利于良好色泽的保持,但是能够很好地控制牛肉的腐败。综合几种冰温结合气调的保鲜技术来看,50%O2结合50%CO2组对牛肉有更好地贮藏保鲜效果。     

Fe3O4-壳聚糖磁性微球的制备及对Cu2+的吸附性能

用壳聚糖包覆羧基化Fe3O4磁性纳米粒子制备了Fe3O4-壳聚糖磁性微球,分别用X-射线衍射、扫描电镜、热重分析等方法和手段对所制备的样品进行了结构表征.利用原子吸收光谱,探讨了时间、pH值、Cu2+浓度等对Fe3O4-壳聚糖磁性微球吸附溶液中Cu2+量的影响.结果表明:Fe3O4-壳聚糖磁性微球粒径分布较均匀,平均粒径约为110 nm;Fe3O4-壳聚糖磁性微球能够吸附Cu2+,最大吸附量可达21.3 mg/g.随着吸附剂用量的增加、温度的升高,单位吸附量减小,室温下吸附较佳;Cu2+初始浓度、pH对吸附的影响很大,Cu2+初始浓度在120 mg/L,5.0相似文献   

Binding of 2,4,6-trinitrotoluene, aniline, and nitrobenzene to dissolved and particulate soil organic matter

The distribution of TNT* (the sum of TNT and its degradation products), aniline, and nitrobenzene between particulate organic matter (POM), dissolved soil organic matter (DOM), and free compound was studied in controlled kinetic (with and without irradiation) and equilibrium experiments with mixtures of POM and DOM reflecting natural situations in organic rich soils. The binding of TNT* to POM was fast, independent of irradiation, and adsorption isotherms had a great linear contribution (as determined by a mixed model), indicative of a hydrophobic partitioning mechanism. The binding of TNT* to DOM was slower, strongly enhanced under nonirradiated conditions, and adsorption isotherms were highly nonlinear, indicative of a specific interaction between TNT derivatives and functional groups of DOM. Nitrobenzene was associated to both POM and DOM via hydrophobic partitioning, whereas aniline binding was dominated by specific binding to POM and DOM functional groups. On the basis of nitrobenzene and TNT* adsorption parameters determined by a mixed Langmuir + linear model, POM had 2-3 times greater density of hydrophobic moieties as compared to DOM. This difference was reflected by a greater (O + N)/C atomic ratio for DOM. The sum of C-C and C-H moieties, as determined by X-ray photoelectron spectroscopy (XPS), and the sum of aryl-C and alkyl-C, as determined by solid-state cross-polarization magic-angle spinning (CP-MAS) 13C NMR, could only qualitatively account for differences in adsorption parameters. Aliphatic C was found to be more important for the hydrophobic partitioning than aromatic C. On the basis of nonlinear adsorption parameters,the density of functional groups reactive with aniline and TNT derivatives was 1.3-1.4 times greater in DOM than in POM, which was in fair agreement with 13C NMR and XPS data for the sum of carboxyl and carbonyl groups as potential sites for electrostatic and covalent bonding. We conclude that in contaminated soils characterized by continuous leaching of DOM, formation of TNT derivatives (via biotic and abiotic reductive degradation) and their preference for specific functional groups in DOM may contribute to a significant transportation of potentially toxic TNT compounds into surface waters and groundwaters.     

Effects of solubility characteristics of sensitiser and pH on the photooxidation of oil in tuna oil-added acidic O/W emulsions

The effects of sensitisers and pH on the oil oxidation of acidic O/W emulsions were studied under light by measuring hydroperoxide content and headspace oxygen consumption in the emulsions. The emulsions consisted of canola and tuna oil (2:1 w/w, 32%), diluted acetic acid (64%), egg yolk powder (4%), chlorophyll b or erythrosine (5 μM), and/or diazabicyclooctane (DABCO) or sodium azide (0.5 M). The emulsion pH values were 2.67, 3.68, and 6.27. Chlorophyll increased oil oxidation in the emulsion under light via singlet oxygen production while erythrosine did not. DABCO significantly decreased photooxidation of the oil containing chlorophyll, suggesting singlet oxygen involvement. However, sodium azide increased photooxidation of the oil containing chlorophyll possibly via azide radical production under acidic conditions. The oil photooxidation was higher in the emulsion containing chlorophyll at pH 6.27 than at pH 2.67 or 3.68, primarily by singlet oxygen and secondarily by free radicals produced from hydroperoxide decomposition.     

Lifetimes of triplet dissolved natural organic matter (DOM) and the effect of NaBH₄ reduction on singlet oxygen quantum yields: implications for DOM photophysics

The natural lifetimes of triplet dissolved organic matter ((3)DOM) were determined by an O(2) saturation kinetics study of singlet oxygen quantum yields (Φ(1O2)) in buffered D(2)O. At least two distinct (3)DOM pools are present, and the observed lifetime range (～20 to 80 μs) leads to a dependence of Φ(1O2) on O(2) concentrations between 29 and 290 μM. Thus, steady-state (1)O(2) concentrations will depend on [O(2)] in natural waters. The lifetimes are essentially identical for DOM samples of different origins and do not vary with excitation wavelength. However, Φ(1O2) varies greatly between samples and decreases with excitation wavelength. These data strongly suggest that (3)DOM quantum yields decrease with excitation wavelength, which gives rise to the Φ(1O2) variation. Borohydride reduction of several samples in both D(2)O and H(2)O lowers the absorbance and (1)O(2) production rates, but it does not alter Φ(1O2). This is consistent with a model in which (1)O(2) sensitizing chromophores are borohydride reducible groups in DOM, such as aromatic ketones. Interpreted in the framework of a charge transfer (CT) model for DOM optical properties, the collective data suggest a model in which electron acceptor moieties are important (1)O(2) sensitizers and where CT interactions of these moieties disrupt their ability to produce (1)O(2).